Utilization of aluminum-chlorid residues



L. S. ABBOTT.

UTILIZATION. OF ALUMINUM CHLORID RESIDUES.

APPLICATION FILED JULY 1. 1919.

Patented Feb. 24, 1920.

Lyle Asa/755027;

UNITED STATES PATENT OFFICE.

LYLE STOCKTON ABBOTT, 0]? PORT ARTHUR, TEXAS, ASSIGNOB TO GULF REFININGCOMPANY, OF PITTSBURGH, PENNSYLVANIA, A CORPORATION OF TEXAS.

UTILIZATION OF ALUMINUM-OHLORID RESIDUES.

Application filed July 1, 1919. Serial No. 308,005.

T 0 all whom it may concern: 7

Be it known that I, LYLE STOCKTON An- BOTT, a citizen of the UnitedStates, residing at Port Arthur, in the county of J ef-" ferson andState of Texas, have invented certain new and useful Improvements in theUtilization of Aluminum-Chlorid Residues, of which the following is aspecification.

This invention relates to the utilization of aluminum chlorid residues;and it comprises a process of obtaining aluminum chlorid from certaincoky, tarry or oily residues formed in various processes of refining,altering and improving oils with aluminum chlorid, wherein such residuesare heated and baked to free them as far as possible ofhydrogen-containing oils and hydrocarbons and are then treated withsuperheated chlorin at a temperature sufiicient to produce and liberatealuminum chlorid, the heat of such superheated chlorin being afforded bythe combustion of excess carbon contamed in such residues, thecombustion of the carbon being either before or after the production ofaluminum chlorid, as by treating heated and baked residues withsuperheated chlorin until such residues are stripped, or substantiallystripped, of aluminum chlorid and bodies capa le of yieldmg aluminumchlorid, thereafter transferring the strlpped carbon to a suitablecombustion chamber and blasting it to incandcscence and superheatingchlorin to be used on such residues by the heat of the incandescentcarbon, or as 'bv blasting up a portion of such residues in a. suitablecombustion chamber to obtain an incandescent heat and passing chlorinthrough the incandescent material, the heated chlorin being thereaftercontacted with another portion of residue; all as more fully hereinafterset forth and as claimed.

There are a number of processes of treating petroleum oils with aluminumchlorid for various purposes, such as the productlon of gasolene, theproductlon of improved lubricating oil, the manufacture of medic naloil, etc., as more fully disclosed 1n various patents to one McAfee (seePatents Nos. 1,127,465, 1,235,523, 1,277,092, 1,277,328 and 1,27 7 ,329,etc). In these processes anhydrous aluminum chlorid is heated wlth theoil under various circumstances to produce various changes in the oil.After a time the activity of the aluminum chlorid as a catalytic agentslackens and ceases; and after a certain time it is removed from thestill or other apparatus and replaced by fresh material. At this time, 1the aluminum chlorid generally occurs in a black, oily; tarry orcoke-like mass. If the various operations utilizing its catalytic powerhave been carrled on with dry oil, substantially free of oxygen andsulfur, the aluminum chlorid'is probably contained as such, that-is,chlorin and aluminum are present in the proper proportions to formaluminum chlorid; but the aluminum chlorid is, so to speak, masked; 1tno longer displays catalytic activity. Possibly this is due to thepresence of inactive compounds of aluminum chlorid with further toliberate and distil ofi' aluminum chlorid.

It is with material of this character that Iv deal in the presentinvention. The aluminum chlorid residues, after freeing from oil as faras possible and baking somewhat, either to break up hydrocarbons or toliberate such aluminum chlorid as can be freed thereby, contain a largeamount of carbon in addition to the residual aluminum chlorid oralumina. In the treatment of some oils, and articularly where anymoisture is present, t ere is, or may be, a considerable amount ofaluminum oxid present. In the present invention, I utilize this carbonfor its fuel value and also recover or utilize the aluminum chlorid andalumina present.

In the manufacture of aluminum chlorid from alumina, carbon and chlorinas usually carried out in the art, alumina and carbon have been placedin retorts situated in a suitably heated furnace and a current ofchlorin passed over. By a well known reaction, aluminum chlorid andcarbon monoxid are formed and the aluminum chlorid, which is in thevapor form, is condensed and separated. In this method of manufacture,however, it is a matter of extreme difiiculty to obtain good reults onany large manufacturing scale, for the reason that the larger the retortthe more intense must be the heat of the walls and it is diflicult'toobtain matelials for making retorts which will withstand the chemicalaction. The production of aluminum chlorid is a heat-absorbing orendothermic reaction and, while it does not require any reat amount ofheat it does require a very i h temperature. uch a temperature is dicult to obtain in the center of a pervious mass contained in a retort ofany large size. In another and copendin ap lication, Serial No. 167,962,May 11, 191 I have described and claimed a method of producing aluminumchlorid from alumina, carbon and chlorin, wherein I carry the necessaryheat units into the mass of carbon and alumina by superheating thechlorin, the chlorin being passed through a space or chamber which isbrought to a high temperature from time to time by producing activecombustion therein. he superheated chlorin carries the necessary numberofheat units and is at a suflicient temperature for effecting thereaction. This obviates the necessity for transmitting heat to thereaction mixture through the walls of 'a' retort. In the stated method,while the temperature necessary may be imparted to a heating chamber,such as a checkerwork, by occasional combustion of air and gas therein,I find it better to use as the heating chamber a structure like anordinary as roducer filled with hot coke or charcoa he coke or charcoalfrom time to time is blastedup to a state of vivid incandescence by acurrent of air. Most advantageously the current of air used in blastingis sent throu h at such a rate of s eed as to produce 0, rather than CO,utilizing the well known principles employed in the blow stage of makmgwater gas. After the blasting up is com leted, the air is cut off andthe exit for b ow gases closed and a current of chlorin is sent directlythrough the incandescent coke and is thereafter passed into a suitablereaction chamber containing briqueted alumina and carbon. In thischamber it produces vapors of aluminum chloridwhich are sent to asuitable condenser. As will be seen, in this specific embodiment of mydescribed method,

two chambers are employed, one serving as a heating up chamber for thechlorin and the other as. a reaction chamber.

I have found this process may be advantion chamber suc as described andpass in superheated chlorin. Under the influence of the chlorin,aluminum chlorid is liberated and formed and passes to a suitablecondensing chamber as just described. Such the residues into .a reac-i.In so doing, the excess of carbon existing in the residues is utilized,efi'ecting an important economy in fuel. The process as just describedmay readily be made continuous, the baked residues being passed througha reaction chamber against a countercurrent 0 of superheated chlorin andthence passing continuously or discontinuously to a suitable combustionchamber wherein the carbon forms a mass which is alternately blastedwith air and utilized in heating chlorin as previously described.

' In an alternative embodiment of the present invention, baked residuemay be charged into the reaction chamber as above and another portion ofresidue charged into the fuel chamber. In the fuel chamber, the residueburns as before to furnish heat which is imparted to chlorin. In theblowing up stage of this residue some of the aluminum chloridcontainedgoes off with the blow gases, usually decomposin therein withde osition of alumina an formation of H 1. Some portion, however,furnishes an incidental amount of aluminum chlorid when the chlorin ispassed through the incandescent mass on its way to the reaction chamber.

In blowing up ignited baked residues with air in order to raise thetemperature of the material, some of the contained aluminum chlorid isdecomposed with loss of chlorin as HCl, a corresponding amount ofalumina being formed. This alumina forms chlorid in the followingtreatment with chlorin. It is therefore advantageous to precede blowingup with a chlorin treatment. In an advantageous embodiment of myinvention I provide a pair of chambers each serving alternately as areaction cham- 7 her and as a heating chamber. In the one temporarilyacting as a reaction chamber, fresh baked residue is subjected to theaction of preheated chlorin coming from the other chamber, temporarilyacting as a heating chamber. After a.time, the supply of- In theaccompanying illustration I have shown, more or less diagrammatically,certain types of apparatus useful in the performance of the describedprocess. In this showing Figure 1 is a central vertical section of onetype of apparatus;

Fig. 2 is a central horizontal section on lines 2-2 of Fig. 1; and

Fig. 3 is a central vertical section of a modified form of apparatus.

In the showing of Figs. 1 and 2, two chambers, marked A and B,respectively intended as a fuel chamber and a reaction chamber, areprovided within a common casing. As shown, steel jacket 1 is lined withfirebrick or the like 2. Another lining 3 is spaced away to some extentand between is'a layer t of heat-insulating material, such askieselguhr. The two chambers communicate at 5 and are separated bypartition 6 which does not extend the full height of the casing. Twoinlets, 8 and 9', for air and for chlorin are provided for the onechamber and two, marked 10 and- 10, for the other. These also serve asoutlets for aluminum chlorid vapors. At the top of the sub-chambers areremovable lids, 11 and at the base removable dumping plates 12.

The structure of Fig. 3 is like that of Fig. 1 (like referencecharacters indicating like elements) differing mainly in that twostructurally separate chambers ar nrovided instead of subdividing onechamber into two sub-chambers. Chamber A has a special outlet 13 andchamber B has a special side door 11.

In the use of these structures, in Fig. 1 chamber B may be filled withbaked residue and air blown into A through 8 until the contents(previously treated residue or coke) are incandescent, products ofcombustion escaping at the top. Top door 11 is removed during thisphase. When the charge in A is sufiiciently heated, the door is replacedand chlorin is introduced through 9. This chlorin passes up through thehot fuel, is heated and passes into B through 5. In B it forms andreleases aluminum chlorid as vapors which pass through 10 to a suitablecondenser (not shown). After a time when the charge B is exhausted, itmay be transferred to A and used for its fuel value.

In another way of using this apparatus, A being supposed to be full offuel and B with baked residues, after the charge in B is substantiallyexhausted, the charge in A may be replaced by fresh residue and thedraft currents reversed, air being first blown in at 10 and then chlorinat 10 while aluminum chlorid passes away to a condenser at 8.

In Fig. 3, after a charge in B has been chlorinated (vapors of aluminumchlorid being removed at 10), it may be transferred to A, side door 11being provided to facilitate this transfer.

What I claim is 1. In the utilization of exhausted aluminum chloridresidues, the process which comprises treating such a residue with acurrent of superheated chlorin, burning a portion of the carboncontained in such a residue to heat the remaining carbon toincandescence and passing the heated chlorin through the incandescentmass to afford the stated preheating.

2. In the utilization of exhausted aluminum chlorid residues, theprocess which comprises treating such a residue in a suitable reactionchamber with preheated chlorin at a temperature sufiicient for theformation of aluminum chlorid in the vapor form until the residue isstripped of aluminum compounds, removing the stripped material from thereaction chamber, blowing it up with air to an incandescent heat andpassing chlorin through the incandescent mass on its way to reactionchamber.

3. The process of recovering aluminum chlorid from oil residues'whichcomprises exposing such residues to a current of preheated chlorin toform aluminum chlorid, thereafter blasting up with air and once morepassing through chlorin to preheat such chlorin.

In testimony whereof I aflix my signature hereto.

LYLE STOCKTON ABBOTT.

